Stabilized hydrochlorofluoroolefins and hydrofluoroolefins

ABSTRACT

Disclosed is a combination of hydrofluoroolefins and/or hydrochlorofluoroolefins with stabilizers wherein the stabilizers minimize the degradation of the hydrofluoroolefins and hydrochlorofluoroolefins during storage, handling and use yet allow for atmospheric degradation. The combinations exhibit low or zero ozone depletion potential and lower global warming potential making them of interest as replacements for chlorofluorocarbons and hydrofluorocarbons. The combinations of the present invention comprise hydrofluoroolefins and/or hydrochlorofluoroolefins in combination with a stabilizer or stabilizers selected from free radical scavengers, acid scavengers, oxygen scavengers, polymerization inhibitors and combinations thereof.

The present application is a continuation-in-part of and claims prioritybenefit U.S. application for patent Ser. No. 13/778,584 filed Feb. 27,2013, which is a continuation of and claims priority benefit of U.S.application for patent Ser. No. 12/664,200 filed Dec. 11, 2009, now U.S.Pat. No. 8,388,857, which claims priority benefit of Internationalapplication for patent serial number PCT/US08/68560 filed Jun. 27, 2008which designated the United States which claims priority benefit of U.S.provisional application Ser. No. 60/946,410 filed Jun. 27, 2007, all ofwhich are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to stabilized hydrochlorofluoroolefin andhydrofluoroolefin compositions wherein the composition comprises afluoroolefin and at least one stabilizing component. The compositions ofthe present invention are useful in processes for producing cooling orheat, as heat transfer fluids, foam blowing agents, aerosol propellants,fire suppression, extinguishing agents and solvent applications.

BACKGROUND OF THE INVENTION

The Montreal Protocol for the protection of the ozone layer, signed inOct. 1987, mandate the phase out of the use of chlorofluorocarbons(CFCs). Materials more “friendly” to the ozone layer, such ashydrofluorocarbons (HFCs) eg HFC-134a replaced chlorofluorocarbons. Thelatter compounds have proven to be green house gases, causing globalwarming and were regulated by the Kyoto Protocol on Climate Change. Theemerging replacement materials, hydrofluoropropene, were shown to beenvironmentally acceptable ie has zero ozone depletion potential (ODP)and low global warming potential (GWP), much less than 150.

Currently proposed replacement refrigerants for hydrofluorocarbons suchas HFC-134a include HFC-152a, pure hydrocarbons such as butane orpropane, or “natural” refrigerants such as CO₂. Many of these suggestedreplacements are, flammable, and/or have low energy efficiency.Therefore, new alternative refrigerants are being sought. Fluoroolefinmaterials such as hydrofluoropropene and/or hydrochlorofluoropropenehave generated interest as replacements for HFCs. The inherent chemicalinstability of these materials in the lower atmosphere provides the lowglobal warning potential and zero or near zero ozone depletionproperties desired. However, such inherent instability is believed toalso impact the commercial application of such materials which willdegrade during storage, handling and use.

The object of the present invention is to provide novel compositionsthat can serve as refrigerant and heat transfer fluids as well asblowing agents, solvent cleaners, aerosol propellant, fire fightingagent, etc. that provide unique characteristics to meet the demands oflow or zero ozone depletion potential and lower global warming potentialas compared to the current HFCs.

SUMMARY OF THE INVENTION

The present invention is directed toward combinations ofhydrofluoroolefins and/or hydrochlorofluoroolefins with stabilizerswherein the stabilizers minimize the degradation of thehydrofluoroolefins and hydrochlorofluoroolefins during storage, handlingand use yet allow for the atmospheric degradation that results in low orzero ozone depletion potential and lower global warming potential. Thecombinations of the present invention comprise hydrofluoroolefins (HFO)and/or hydrochlorofluoroolefins (HCFO) in combination with a stabilizerselected from free radical scavengers, acid scavengers, oxygenscavengers, corrosion inhibitor, polymerization inhibitors andcombinations thereof.

DESCRIPTION OF THE INVENTION

The present invention is directed towards combinations which providehydrofluoroolefins (HFO) and/or hydrochlorofluoroolefins (HCFO) whichare chemically stable during use, storage and transportation but will bedegrade in the troposphere (tropodegradable). The inventive combinationprovides hydrofluoroolefins and/or hydrochlorofluoroolefins for use asheat transfer fluids, blowing agents, solvent cleaners for metaldegreasing and dewatering, fire fighting agents and aerosol propellants,which exhibit a low global warming potential GWP (less than 150) andzero or near zero ozone depletion potential ODP. Hydrofluoroolefinsand/or hydrochlorofluoroolefins have been proposed as heat transferfluids as well as blowing agents, solvent cleaners etc. which exhibit alow global warming potential and a low ozone depletion value. Examplesof linear hydrofluoroolefins and hydrochlorofluoroolefins include butnot limited to: 1225ye E and Z isomers (CF₃—CF═CFH), 1234ze E and Zisomers (CF₃—CH═CHF), 1234yf (CF₃—CF═CH₂), 1233zd E and Z isomers(CF₃—CH═CHCl), 1.233xf (CF₃—CCl═CH₂) and isomers of 1223za (CF₃—CH═Cl₂)and 1223xd (CF₃—Cl═CHCl E and Z) alone or in combination.

The low global warming potential and a low ozone depletion value are aresult of the atmospheric degradation of the hydrofluoroolefins and/orhydrochlorofluoroolefins by reaction with the hydroxyl radical OH. inthe lower troposphere. Equally important; is to maintain chemicalstability of the proposed HFO and HCFO during actual applications.Because of the presence of alkene linkage it is expected that the HFOsand HCFOs will be chemically unstable, relative to processor HCFC orCFC. The inventors have discovered that HFOs such as 1234ze caneliminate HF to form trifluoropropyne, during the production ofpolystyrene foam (XPS) or polyurethane foam (PUR).

The present inventors have discovered that hydrofluoroolefins and/orhydrochlorofluoroolefins can be stabilized against degradation duringuse, storage and handling by the addition of a stabilizer or stabilizersselected from free radical scavengers, acid scavengers, oxygenscavengers, polymerization inhibitors, corrosion inhibitors andcombinations thereof. The stabilizers of the present invention haveminimal impact on the degradation of the hydrofluoroolefins and/orhydrochlorofluoroolefins when released into the atmosphere. Exemplarystabilizers include but are not limited to: 1,2-epoxybutane; glycidylmethyl ether; d,l-limonene; d,l-limonene oxide;1,2-epoxy-2-methylpropane; nitromethane; diethylhydroxylamine;alpha-methylstyrene; isoprene; p-methoxyphenol; 3-methoxyphenol;hydrazines; 2,6-di-t-butylphenol and hydroquinone.

The hydrofluoroolefin and/or hydrochlorofluoroolefin combinations of thepresent invention are tropodegradable while at the same time theyprovide chemical stability during use, storage and shipping. Stabilityof the combinations of the present invention is evidenced by thepresence of no more than 0.1% (1000 ppm) of impurities in thecombination after aging. It is believed that the combinations provide“application” stability by controlling the formation of undesirablereactants such as oxygenated products, acids, radicals and corrosioninitiators in the presence of active metals, oxygen containingcompounds, moisture and during exposure to high temperatures andpressures. The level of the stabilizer component of the combination ofthe present invention can range from about 1 to 50,000 ppm, preferablyabout 100 ppm to 1000 ppm of the combination. The hydrofluoroolefinsand/or hydrochlorofluoroolefins combinations have a zero or near zeroozone depletion value, a low (less than about 150) global warmingpotential, are non-flammable, non-toxic or of low toxicity. The stablehydrofluoroolefin and or hydrochlorofluoroolefins of the presentinvention can he used in various applications such as:

-   1. Mobil Air Conditions (MAC) and Other Refrigerant Applications:

A refrigerant must be chemically stable during the refrigeration cycleeg, (a) resistant to reaction with active metal in the system such asiron, aluminum and copper causing corrosion: (b) resistant to chemicalreactions such as dimerization/polymerization or which generatecorrosive acids such as HF and/or HCl under the operating pressure andtemperature. Furthermore, a refrigerant must be soluble and compatiblewith refrigerant oil(s).

The hydrofluoroolefins and/or hydrochlorofluoroolefins with stabilizercombinations of the present invention have been found effective asreplacements for high GWP refrigerant(s) in refrigeration,air-conditioning, or heat pump systems. Conventional high GWPrefrigerants in such systems include materials such as R134a, R22,R245fa, R114, R236fa, R124, R410A, R407C, R417A, R422A, R507A, andR404A. The hydrofluoroolefins and/or hydrochlorofluoroolefins withstabilizer combinations of the present invention are effective workingfluids in refrigeration, air-conditioning, or heat pump apparatus thatuses, used or is designed to use conventional high GWP refrigerants,

Vapor-compression refrigeration, air-conditioning, or heat pump systemsinclude an evaporator, a compressor, a condenser, and an expansiondevice. A vapor-compression cycle re-uses refrigerant in multiple stepsproducing a cooling effect in one step and a heating effect in adifferent step. The cycle can be described simply as follows: liquidrefrigerant enters an evaporator through an expansion device, and theliquid refrigerant boils in the evaporator at a low temperature to forma gas and produce cooling. The low-pressure gas enters a compressorwhere the gas is compressed to raise its pressure and temperature. Thehigher-pressure (compressed) gaseous refrigerant then enters thecondenser in which the refrigerant condenses and discharges its heat tothe environment. The refrigerant returns to the expansion device throughwhich the liquid expands from the higher-pressure level in the condenserto the low-pressure level in the evaporator, thus repeating the cycle.

As used herein, mobile refrigeration apparatus or mobileair-conditioning (MAC) apparatus refers to any refrigeration orair-conditioning apparatus incorporated into a transportation unit forthe road, rail, sea or air. The present invention is particularly usefulfor road transport refrigerating or air-conditioning apparatus, such asautomobile air-conditioning apparatus or refrigerated road transportequipment.

The hydrofluoroolefins and/or hydrochlorofluoroolefins with stabilizercombinations of the present invention may also be useful in stationaryair-conditioning and heat pumps, e.g. chillers, high temperature heatpumps, residential and light commercial and commercial air-conditioningsystems, in stationary refrigeration applications, the presentcompositions may be useful in equipment such as domestic refrigerators,ice machines, walk-in and reach-in coolers and freezers, and supermarketsystems.

When used as refrigerants, the hydrofluoroolefin and/orhydrochlorofluoroolefin combinations of the present invention typicallywill include refrigeration lubricants, i.e. those lubricants suitablefor use with refrigeration, air-conditioning, or heat pump apparatus.Among these lubricants are those conventionally used in compressionrefrigeration apparatus utilizing chlorofluorocarbon refrigerants. Suchlubricants and their properties are discussed in the 1990 ASHRAEHandbook, Refrigeration Systems and Applications, chapter 8, titled“Lubricants in Refrigeration Systems”. Lubricants of the presentinvention may comprise those commonly known as “mineral oils” in thefield of compression refrigeration lubrication, mineral oils compriseparaffins (i.e. straight-chain and branched-carbon-chain, saturatedhydrocarbons), naphthenes (i.e. cyclic paraffins) and aromatics (i.e.unsaturated, cyclic hydrocarbons containing one or more ringscharacterized by alternating double bonds). Lubricants of the presentinvention further comprise those commonly known as “synthetic oils” inthe field of compression refrigeration lubrication. Synthetic oilscomprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes),synthetic paraffins and napthenes, and poly(alphaolefins). Lubricants ofthe present invention further comprise those that have been designed foruse with hydrofluorocarbon refrigerants and are miscible withrefrigerants of the present invention under compression refrigeration,air-conditioning, or heat pump apparatus operating conditions. Suchlubricants include, but are not limited to, polyol esters (POEs) such asCastrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) suchas RL-488A from Dow (Dow Chemical, Midland, Mich.), and polyvinyl ethers(PVEs). These lubricants are readily available from various commercialsources.

Lubricants of the present invention are selected by considering a givencompressor's requirements and the environment to which the lubricantwill be exposed. Commonly used refrigeration system additives mayoptionally be added, as desired, to compositions of the presentinvention in order to enhance lubricity and system stability. Theseadditives are generally known within the field of refrigerationcompressor lubrication, and include anti wear agents, extreme pressurelubricants, corrosion and oxidation inhibitors, metal surfacedeactivators, foaming and antifoam control agents, leak detectants andthe like. In general, these additives are present only in small amountsrelative to the overall lubricant composition. They are typically usedat concentrations of from less than about 0.1% to as much as about 3% ofeach additive. These additives are selected on the basis of theindividual system requirements. Some typical examples of such additivesmay include, but are not limited to, lubrication enhancing additives,such as alkyl or aryl esters of phosphoric acid and of thiophosphates.Additionally, the metal dialkyl dithiophosphates and other members ofthis family of chemicals may be used in compositions of the presentinvention. Other antiwear additives include natural product oils andasymmetrical polyhydroxyl lubrication additives such as Synergol TMS(International Lubricants).

-   2. Blowing Agents

Thermoset foams such as rigid polyurethane foams can be prepared bymixing, under controlled conditions, MDI, polyols, blowing agents andadditives i.e. catalysts, surfactants, water, and fire retardants.Different type of polyols can be used, typically in combination withpolymeric MDI, and additives are typically preblended into the polyol.The formation of highly cross-linked homogeneous glassy networkstructure is essential for the final properties of the resulting foam.These properties include good heat stability, high compression strengthat low density and good barrier properties.

In order to achieve optimum processing and end properties simultaneouslya large number of formulations are required. One of key properties ofrigid polyurethane foam is low thermal conductivity that is achieved byproducing fine and closed-cell foam of the required density using waterand a physical co-blowing agent. The physical blowing agent needs tohave a low thermal conductivity as it stays in the cells and contributesto the level and stability of thermal conductivity of the foams.

For rigid polyurethane foam the initial exothermic reaction is normallybetween isocyanate and water, leading to the formation of am amine andcarbon dioxide; the amine then reacts with more isocyanate to formpolyurea. The other key exothermic reactions are between isocyanate andpolyol, producing polyurethane and isocyanate trimerisation. Appropriatecatalysts are selected for specific functions, such as, blowing, gellingand trimerisation to control the overall reaction rates and balanceamong them.

Once the isocyanate and polyol blend are thoroughly mixed there isnormally a 30-fold increase in volume upon reaction and the formation ofindividual cell is related to the presence of nuclei in the mixture.Cell formation and stabilization are also related to the rightsurfactant. The rigid foam polymer structure becomes self-supportingonce enough network formation has established.

The center of the foam can reach temperatures as high as 190° C. due tothe exothermic reactions, however, the reaction are not completed at theend of foam rise and can go on for many hours. Similarly, it can severalday for the center of the foam to completely cool down to ambienttemperature.

The blowing agent combinations of the present invention can be used as afoaming agent for polyurethane foams by being mixed in a polyol mixture(typically referred to as the B side) which form foam when mixed with apolymeric MDI mixture (typically referred to as the A side).

For the production of thermoplastic foams, the preferred combinations ofthe present invention will have boiling points less than the melt and/orglass transition temperature of the polymer resin, typically less thanabout 100° C., preferably between about −40° C. to about 10° C.

The process for preparing a foamed thermoplastic product is as follows:Prepare a foamable polymer composition by blending together componentscomprising foamable polymer composition in any order. Typically, preparea foamable polymer composition by plasticizing a polymer resin and thenblending in components of a blowing agent composition at an initialpressure. A common process of plasticizing a polymer resin is heatplasticization, which involves heating a polymer resin enough to softenit sufficiently to blend in a blowing agent composition. Generally, heatplasticization involves heating a thermoplastic polymer resin near orabove its glass transition temperature (Tg), or melt temperature (Tm)for crystalline polymers.

A foamable polymer composition can contain additional additives such asnucleating agents, cell-controlling agents, dyes, pigments, fillers,antioxidants, extrusion aids, stabilizing agents, antistatic agents,fire retardants, IR attenuating agents and thermally insulatingadditives. Nucleating agents include, among others, materials such astalc, calcium carbonate, sodium benzoate, and chemical blowing agentssuch azodicarbonamide or sodium bicarbonate and citric acid. IRattenuating agents and thermally insulating additives include carbonblack, graphite, silicon dioxide, metal flake or powder, among others.Flame retardants can include, among others, brominated materials such ashexabromocyclodecane and poly brominated biphenyl ether.

Foam preparation processes of the present invention include batch,semi-batch, and continuous processes. Batch processes involvepreparation of at least one portion of the foamable polymer compositionin a storable state and then using that portion of foamable polymercomposition at some future point in time to prepare a foam.

A semi-batch process involves preparing at least a portion of a foamablepolymer composition and intermittently expanding that foamable polymercomposition into a foam all in a single process. For example, U.S. Pat.No. 4,323,528, herein incorporated by reference, discloses a process formaking polyolefin foams via an accumulating extrusion process. Theprocess comprises: 1) mixing a thermoplastic material and a blowingagent composition to form a foamable polymer composition; 2) extrudingthe foamable polymer composition into a holding zone maintained at atemperature and pressure which does not allow the foamable polymercomposition to foam; the holding zone has a die defining an orificeopening into a zone of lower pressure at which the foamable polymercomposition foams and an openable gate closing the die orifice; 3)periodically opening the gate while substantially concurrently applyingmechanical pressure by means of a movable ram on the foamable polymercomposition to eject it from the holding zone through the die orificeinto the zone of lower pressure, and 4) allowing the ejected foamablepolymer composition to expand to form the foam.

A continuous process involves forming a foamable polymer composition andthen expanding that foamable polymer composition in a non-stop manner.For example, prepare a foamable polymer composition in an extruder byheating a polymer resin to form a molten resin, blending into the moltenresin a blowing agent composition at an initial pressure to form afoamable polymer composition, and then extruding that foamable polymercomposition through a die into a zone at a foaming pressure and allowingthe foamable polymer composition to expand into a foam. Desirably, coolthe foamable polymer composition after addition of the blowing agent andprior to extruding through the die in order to optimize foam properties.Cool the foamable polymer composition, for example, with heatexchangers.

Foams of the present invention can be of any form imaginable includingsheet, plank, rod, tube, beads, or any combination thereof. Included inthe present invention are laminate foams that comprise multipledistinguishable longitudinal foam members that are bound to one another.

In another embodiment, the present invention relates to blowing agentcompositions comprising the hydrofluoroolefins and/orhydrochlorofluoroolefins with stabilizer combinations as describedherein for use in preparing foams. In other embodiments the inventionprovides foamable compositions, and preferably polyurethane,polyisocyanate and thermoplastic foam compositions such as EPS and XPSfoams, and method of preparing foams. In such foam embodiments, one ormore of the present hydrofluoroolefins and/or hydrochlorofluoroolefinswith stabilizer combinations are included as a blowing agent in foamablecompositions, which composition preferably includes one or moreadditional components capable of reacting and foaming under the properconditions to form a foam or cellular structure. Any of the methods wellknown in the art may be used or adapted for use in accordance with thefoam embodiments of the present invention.

The present invention further relates to a method of forming a foamcomprising: (a) adding to a foamable composition a hydrofluoroolefinsand/or hydrochlorofluoroolefins with stabilizer combinations of thepresent invention; and (b) reacting the foamable composition underconditions effective to form a foam.

The hydrofluoroolefins and/or hydrochlorofluoroolefins of the presentinvention include open chain C₂, C₃ and C₄ hydrochlorofluoroolefins ofthe general formula C_(n)H_(2n-a-b)F_(a)Cl_(b) where n=3-8 and b=0-3 anda=0-14 and 2n is greater than a+b

-   -   cyclic C₃ to C₅ hydrochlorofluoroolefins of the general formula        C_(n)H_(2n-2a-x-y)F_(a)Cl_(b) where n=3, 4 or 5, x=0-7, y=0-3,        and a is the number of unsaturated double bonds, a=2n−2a≧x+y.

The stabilizing component of the hydrofluoroolefins and/orhydrochlorofluoroolefins with stabilizer combinations of the presentinvention comprise one or more free radical scavengers, acid scavengers,oxygen scavengers, polymerization inhibitors, corrosion inhibitors andcombinations thereof. Exemplary acid scavengers include but are notlimited to 1,2-epoxy butane; glycidyl methyl ether; d,l-limonene oxide;1,2-epoxy-2,2-methylpropane and nitroalkanes such as nitromethane.Exemplary oxygen scavengers include but are not limited to alphamethylsytrene and isoprene. Exemplary polymerization inhibitors includebut are not limited to d,l-limonene and isoprene.

The linear hydrofluoroolefins and/or hydrochlorofluoroolefins compoundsof the present invention can include HFC-1225ye, HFC-1234ze, HFC-1234yf,1233zd, 1243zf, 1233xf, 1223za, 1223xd and the similar materials,according to the formula listed above for open chain and cycliccompounds. The hydrofluoroolefins and/or hydrochlorofluoroolefins mayexist as different optical isomers or geometrical isomers. The presentinvention is intended to include all geometric isomers and opticalisomers or any combination or mixture thereof. For instance,1,3,3,3-tetra-fluoropropene (HFC-1234ze) is meant to represent thecis-isomer, trans-isomer or any combination or mixture of both isomersin any ratio. Another example is HFC-1225ye, by which is represented thecis-isomer, trans-isomer, or any combination or mixture of both isomersin any ratio.

-   3. Aerosol Propellants:

Another embodiment of the present invention relates to the use of thehydrofluoroolefins and/or hydrochlorofluoroolefins with stabilizercombinations as described herein for use as propellants in sprayablecompositions. Additionally, the present invention relates to a sprayablecomposition comprising the hydrofluoroolefins and/orhydrochlorofluoroolefins with stabilizer combinations as describedherein. The active ingredient to be sprayed together with inertingredients, solvents and other materials may also be present in asprayable composition. Preferably, the sprayable composition is anaerosol. Suitable active materials to be sprayed include, withoutlimitations, cosmetic materials, such as deodorants, perfumes, hairsprays, cleaners, and polishing agents as well as medicinal materialssuch as anti-asthma and anti-halitosis medications.

The present invention further relates to a process for producing aerosolproducts comprising the step of adding a hydrofluoroolefins and/orhydrochlorofluoroolefins with stabilizer combinations as describedherein to active ingredients in an aerosol container, wherein saidcomposition functions as a propellant.

-   4. Fire Fighting Agents:

A further embodiment provides methods of extinguishing or suppressing afire in a total-flood application comprising providing an agentcomprising a hydrofluoroolefins and/or hydrochlorofluoroolefins withstabilizer combinations of the present invention; disposing the agent ina pressurized discharge system; and discharging the agent into an areato extinguish or suppress fires in that area. Another embodimentprovides methods of inerting an area to prevent a fire or explosioncomprising providing an agent comprising a hydrofluoroolefins and/orhydrochlorofluoroolefins with stabilizer combinations of the presentinvention; disposing the agent in a pressurized discharge system; anddischarging the agent into the area to prevent a fire or explosion fromoccurring,

The term “extinguishment” is usually used to denote complete eliminationof a fire; whereas, “suppression” is often used to denote reduction, butnot necessarily total elimination, of a fire or explosion. As usedherein, terms “extinguishment” and “suppression” will be usedinterchangeably. There are four general types of halocarbon fire andexplosion protection applications. (1) In total-flood fireextinguishment and/or suppression applications, the agent is dischargedinto a space to achieve a concentration sufficient to extinguish orsuppress an existing fire. Total flooding use includes protection ofenclosed, potentially occupied spaces such, as computer rooms as well asspecialized, often unoccupied spaces such as aircraft engine nacellesand engine compartments in vehicles. (2) In streaming applications, theagent is applied directly onto a fire or into the region of a fire. Thisis usually accomplished using manually operated wheeled or portableunits. A second method, included as a streaming application, uses a“localized” system, which discharges agent toward a fire from one ormore fixed nozzles. Localized systems may be activated either manuallyor automatically. (3) in explosion suppression, a hydrofluoroolefinsand/or hydrochlorofluoroolefins with stabilizer combinations of thepresent invention is discharged to suppress an explosion that hasalready been initiated. The term “suppression” is normally used in thisapplication because the explosion is usually self-limiting. However, theuse of this term does not necessarily imply that the explosion is notextinguished by the agent. In this application, a detector is usuallyused to detect an expanding fireball from an explosion, and the agent isdischarged rapidly to suppress the explosion. Explosion suppression isused primarily, but not solely, in defense applications. (4) Ininertion, a hydrofluoroolefins and/or hydrochlorofluoroolefins withstabilizer combinations of the present invention is discharged into aspace to prevent an explosion or a fire from being initiated. Often, asystem similar or identical to that used for total-flood fireextinguishment or suppression is used. Usually, the presence of adangerous condition (for example, dangerous concentrations of flammableor explosive gases) is detected, and the hydrofluoroolefins and/orhydrochlorofluoroolefins with stabilizer combinations of the presentinvention is then discharged to prevent the explosion or fire fromoccurring until the condition can be remedied.

The extinguishing method can be carried out by introducing thecomposition into an enclosed area surrounding a fire. Any of the knownmethods of introduction can be utilized provided that appropriatequantities of the composition are metered into the enclosed area atappropriate intervals. For example, a composition can be introduced bystreaming, e.g. using conventional portable (or fixed) fireextinguishing equipment; by misting; or by flooding, e.g., by releasing(using appropriate piping, valves, and controls) the composition into anenclosed area surrounding a fire. The composition can optionally becombined with an inert propellant, e.g., nitrogen, argon, decompositionproducts of glycidyl azide polymers or carbon dioxide, to increase therate of discharge of the composition from the streaming or floodingequipment utilized.

Preferably, the extinguishing process involves introducing ahydrofluoroolefins and/or hydrochlorofluoroolefins with stabilizercombinations of the present invention to a fire or flame in an amountsufficient to extinguish the fire or flame. One skilled in this fieldwill recognize that the amount of flame suppressant needed to extinguisha particular fire will depend upon the nature and extent of the hazard.When the flame suppressant is to be introduced by flooding, cup burner,test data is useful in determining the amount or concentration of flamesuppressant required to extinguish a particular type and size of fire.

-   5. Solvent:

The ideal hydrochlorofluoroolefin and for hydrofluoroolefin, suitablefor solvent applications, should have a boiling point between about10-60° C. The product should be chemically stable in contact with metalsand resistant to swelling upon exposure to various plastic such asacrylonitrile butadiene styrene, PVC, polybutyelene tetraphathlate,polyethylene HD, polyethylene LD, polymethyle methacrylate,polyethylene, high impact polystyrene, polystyrene crystals, polystyrene1160, polypropylene, polyamide 11, polycarbonate, polyvinylidenefluoride, polyetehrer block amide; or elastomeric material such asstyrene butadiene 6510, ethylene propylene EP710, hydrogenatednitrile7DT1566, polychloroprene N658, polyacrylates DA 65, hyplalonDH70, fluorocarbon df, nitrile PB701, silicone SL1002, polyisoprenepolybutadiene c6514, Teflon® 62945R.

EXAMPLES Examples 1-4 Stability of 1234ze, 1.233zd, 1243zf and F1233xfas a Blowing Agent in PUR Formulation

Foam was made by small polyurethane dispenser consisting of twopressurized cylinders, one for the A side methylene diphenyldiisocyanate (MDI) and one for the B side (polyol mixtures). Thepressure in the cylinders could be adjusted by regulators. The B-sidemixtures were pre-blended and then charged into the pressurizedcylinders. The blowing agents were then added into B-side cylinder andmixed thoroughly. The cylinders were connected to a dispensing gunequipped with a static mixer. The pressures of both cylinders wereadjusted so that desired ratio of the A and B sides could be achieved.The formulations tested (all had an Iso Index of 110) contained RubinateM, a polymeric methylene diphenyl diisocyanate (MDI) available fromHuntsman; Jeffol SG-360 and R-425-X, polyols from Huntsman; TEAP-265, apolyol from Carpenter Company; Tegostab B 8465 a surfactant availablefrom Evonik-Degussa; Jeffcat TD33A and ZR-70, catalysts available fromHuntsman; NP 9.5, a compatibilizer available from Huntsman. The totalblowing agent level was 26.0 mls/g. Table 1 summarizes the formulationsof the study.

TABLE 1 B side and A side combinations used in making PUR foam.Formulation (wt %) Example 1 Example 2 Example 3 Example 4 Jeffol SG-36015.10 15.45 14.77 14.77 Jeffol R-425-X 4.31 4.41 4.22 4.22 TEAP-265 8.638.83 8.44 8.44 DEG 2.16 2.21 2.11 2.11 Jeffcat TD33A 0.23 0.23 0.23 0.23Jeffcat ZR70 0.23 0.23 0.23 0.23 NP 0.5 6.50 6.50 6.50 6.50 Water 0.420.42 0.42 0.42 HFO-1234ze 10.57 0 0 0 HFO-1243zf 0 8.92 0 0 HCFO-1223zd0 0 12.11 0 HCFO-1233xf 0 0 0 12.11 Rubinate M 50.95 51.89 50.08 50.08A/B 1.04 1.08 1.02 1.06

The cell gases of the foams made using set out in Table 1, were analyzedby crushing a piece the foam inside a gas tight syringe and analyzingthe gas. The results are summarized in Table 2.

TABLE 2 Foam Gas Analysis % Blowing Example 1 Example 2 Example 3Example 4 agents Before¹ After² Before After Before After Before After1234ze 99.96% 99.66% 5090 4014 138 13.7 1233zd 99.2% 99.2% 20 1243zf99.96% 99.91% 173 1233xf 99.95% 99.95% Trifluoropropyne 27.5 43.5SiMe2F2 2336 6 6 0 SiMe3F 239 63 0 6 others 0.04 ¹Indicate the % purityof starting material. Product may contains other impurities expressed inPPM ²Indicate the % purity of the starting material after making foam.

The data in Table 2 shows that 1234ze underwent significant degradationduring the process of making PUR foam. The level of degradation isapproximately 2336 ppm as shown by the formation ofdifluorodimethylsilane and fluorotrimethylsilane. The presence of theseco-products, results from the elimination of HF and with the formationof trifluoropropyne. The HF produced in the process reacts with thesilicone surfactant, present in the B side formulation, to produce thetwo silane products, difluorodimethylsilane and fluorotrimethylsilane.

The data in table 2 shows that 1234ze is more unstable than 1233zd and1243zf during the process of making PUR foam. This is also confirmed bydata in Example 3, which shows that only the 5090 ppm level of 1234zeimpurity in the 1233zd was decreased to 4041 ppm of. This decreaseappeared as 27.5 of trifluoropropyne. Also, in the case of 1233xf, onlythe 138 ppm of 1234ze was decreased to 13.7 ppm. This decrease appearedas 43.5 ppm of trifluoropropyne.

Example 5 Stability of 1234ze in PUR Foam

Example 2 could be repeated with the addition of 200 ppm of the variousstabilizers listed in Table 3 to the B side formulation and HFO 1234zeused as a foam blowing agent. Table 3 summarizes the expected formationof the silane co-products, which would evidence the degradation of the1234ze.

TABLE 3 Effect of Stabilizers on PUR Foam and HFO 1234ze Blowing AgentStabilizer (200 ppm) Silane Co-Products (ppm) None   2500α-methylstyrene <<100 Nitromethane <<100 1,2-epoxybutane <<100 Glycidylmethyl ether <<100 isoprene <<200

The data would be expected to show that the level of degradation wassubstantially decreased from 2500 ppm of SiF₂Me₂ and SiFMe₃ to much lessthan 100 ppm of the silane compounds.

Example 6-7 Stability of 1243zf and 1234ze in Polystyrene Foam (XPS)

The stability of these blowing agents was investigated in an autoclavein the presence of polystyrene beads and other additives which mimic:the process of making XPS foam.

To an autoclave was added: general purpose polystyrene resin (MFI=11.0g/10 min), talc concentrate (50% talc in polystyrene), water and flameretardant (tris(2-chloroethyl)phosphate). The autoclave was then sealedand loaded with the hydrofluoroolefin to be tested. One “blank” was runwith no hydrofluoroolefin addition and overpressured to 30 psig withnitrogen to permit sampling of the vapor space following aging. Table 4summarizes the formulations tested using 1243zf (example 6) and 1234ze(example 7) as blowing agents. The vapor phase in the autoclave wasanalyzed via gas chromatograph after aging for 24 hours at 140° C. Table5 summarizes the results of the aging testing.

TABLE 4 Formulations of the HFO 1234zf and 1234ze in XPS¹ Poly- Flamestyrene Talc Water Retardant 1234xf 1234ze Example (grams) (grams)(grams) (grams) (grams) (grams) Blank 73.51 3.01 1.54 1.52 0 0 HFO1243zf73.52 3.01 1.51 1.52 8 0 HFO1234ze 73.51 3.01 1.51 1.50 0 10

TABLE 5 Vapor Analysis HFO-1243zf HFO-1234ze Original After AgingOriginal After Aging HFO 99.96 99.96 99.963 99.5333,3,3-trifluoropropyne / / 0.028 0.233 HFC-245fa / / 0 0.097

The vapor analysis of example 5 using HFO 1243zf showed no significantdifference in the vapor composition before or after aging, and the HFO1243zf purity remained at 99.96%.

Table 5 shows the vapor analysis of example 6, where the3,3,3-trifluoropropyne and HFC-245fa are evolved through thedehydrofluorination and hydrofluorination of HFO-1234ze respectively.

Example 8 Effect of Stabilizers on 1234ze Degradation in XPS Foams

Example 7 with 1234ze could be repeated in the presence of 200 ppm ofvarious stabilizers. The level of degradation would be expected to besignificantly reduced as evidenced by a reduction in formation oftrifluoropropyne from approximately 2300 ppm to much less than 100 ppm.Table 7 summarizes expected results.

TABLE 7 Effect of inhibitors on the stabilizations of 1234ze in the XPSformulations Stabilizer (200 ppm) Trifluoropropyne None   2300α-methylstyrene <<100 Nitromethane <<100 1,2-epoxybutane <<100 Glycidylmethyl ether <<100 Isoprene <<200

Examples 9 Through 19

Autoclaves containing E-1233zd and 0.1 wt % of the stabilizers set outin Table 8 were been aged for 10 days@150° C. and then analyzed by GasChromatograph to quantify the amount of Z-1233zd. The data is Table 8 isthe average of duplicate tests.

TABLE 8 Effect of Stabilizers on stability of E-1233zd Wt % of Wt % ofZ-1-chloro- E-1-chloro- 3,3,3-tri- 3,3,3-tri- fluoropropenefluoropropene Example 9 Un-aged Material <0.05 >99.95 Example 10 nostabilizer 4.4 95.6 Example 11 nitromethane 3.8 96.2 Example 121,2-epoxybutane 2.3 97.7 Example 13 Imidazole 1.6 98.4 Example 14limonene 1.55 98.45 Example 15 alpha-methylstyrene <0.05 >99.95 Example16 limonene oxide <0.05 >99.95 Example 17 p-methoxyphenol <0.05 >99.95Example 18 4-tert-butylcatechol <0.05 >99.95 Example 192,6-di-tertbutylphenol <0.05 >99.95

The data in Table 8 shows that radical scavengers comprised of a benzenering having an unsaturated or —OH substitution prevented degradation ofthe E-1233zd in this accelerated aging test, that is stabilized thecombination. Example 10 shows that with no stabilizer, more that 4.4 wt% of impurities form with ageing. Examples 16-19 show that when astabilizer comprising a benzene ring having an unsaturated or —OHsubstitution was added to the E-1-chloro-3,3,3-trifluoropropene, thelevel of impurities after aging was below 0.05 wt %.

While the present invention has been described with respect toparticular embodiments thereof, it is apparent that numerous other formsand modifications of this invention will be obvious to those skilled inthe art. The appended claims and this invention generally should beconstrued to cover all such obvious forms and modifications which arewithin the true spirit and scope of the present invention.

What is claimed is:
 1. A combination comprising ahydrochlorofluoroolefin and a stabilizer consisting of a benzene ringsubstituted with an unsaturated or —OH group selected from the groupconsisting of alpha-methylstyrene, limonene oxide, p-methoxyphenol,4-tert-butylcatechol, 2,6-di-terbutylphenol and mixtures thereof.
 2. Thecombination of claim 1 wherein said hydrochlorofluoroolefin is selectedfrom the group consisting of 1233zd (CF₃—CH═CHCl), 1233xf (CF₃—CCl═CH₂)and mixtures thereof.
 3. The combination of claim 1 wherein saidstabilizer is present in an amount of from about 1 to 50,000 ppm.
 4. Thecombination of claim 1 wherein said stabilizer is present in an amountof from about 100 to 1,000 ppm.
 5. A heat transfer fluid compositioncomprising a hydrochlorofluoroolefin and a stabilizer consisting of abenzene ring substituted with an unsaturated or —OH group selected fromthe group consisting of alpha-methylstyrene, limonene oxide,p-methoxyphenol, 4-tert-butylcatechol, 2,6-di-terbutylphenol andmixtures thereof.
 6. The combination of claim 5 wherein saidhydrochlorofluoroolefin is selected from the group consisting of 1233zd(CF₃—CH═CHCl), 1233xf (CF₃—CCl═CH₂) and mixtures thereof.
 7. Thecombination of claim 5 wherein said stabilizer is present in an amountof from about 1 to 50,000 ppm.
 8. The combination of claim 5 whereinsaid stabilizer is present in an amount of from about 100 to 1,000 ppm.9. The combination of claim 6 wherein less than 0.1 wt % of Z-1233zdforms after ageing E-1233zd and said stabilizer for 24 hours at 140° C.